Process to modify polymeric materials and resulting compositions

ABSTRACT

Disclosed is a method for modifying a polymer by carrying out a thermally-induced reaction in a mixing apparatus having a high shear environment and devolatilization capabilities. Also disclosed are the resulting materials.

FIELD OF INVENTION

[0001] The present invention relates to a process for the modificationof polymeric materials.

BACKGROUND

[0002] The modification of polymers can produce materials withconsiderable commercial applicability, finding uses as dispersants,blend compatibilizers, surfactants, surface modifiers, colloidalstabilizers, stain release agents, encapsulants, binding agents,viscosity modifiers, and (in some cases) precursors to ionomers.Important synthetic targets within this area are polymers containingcarboxylic acid, hydroxyl, amine or thiol segments, due to their highpolarity and water miscibility.

[0003] Additionally, modified materials containing hydroxyl or (moreimportantly) acid/anhydride functional groups are of interest forreactive grafting or blending applications, due to the ability of theanhydride to interact with monomeric or oligomeric amines and alcoholsresulting in grafted block copolymers. Reactive blend compatibilizationcan also be achieved through use of these functional block copolymers.

SUMMARY OF THE INVENTION

[0004] An ongoing need exists for an efficient and controlled processfor synthesizing polymers via modification. Modification includesrearrangement of a polymer molecule and deprotection of protectedsegments of a polymer to expose a reactive functional group. A moietymay then, optionally, be grafted onto the functional group. The abilityto efficiently and cleanly modify a polymer in a cost-effective processthat can be easily scaled up is needed. The present invention addressesthese needs.

[0005] Briefly, one aspect of the present invention provides a methodfor modifying a polymer comprising: providing a mixing apparatus havinga high shear environment and devolatilization capabilities, introducinginto the apparatus a composition containing at least one polymer thatcan be modified by a thermally-induced reaction, exposing thecomposition to the high shear environment at a temperature of about 100°C. to about 180° C., whereby a thermally-induced reaction occurs andvolatile by-product is removed.

[0006] The composition may comprise 90 weight % solids or less whenintroduced into the apparatus. The composition may comprise at least onepolymer that is temperature sensitive.

[0007] The thermally-induced reaction may remove at least one protectivegroup to expose a functional group, which may be capable of undergoing agrafting reaction. The functional group may be ethylenically oracetylenically unsaturated. Subsequently, an in situ chemical reactionat the functional group may occur. For example, a graft polymer may beformed.

[0008] Virtually any thermally-induced reaction may be carried out perthe present invention. The thermally-induced reaction may comprises theelimination of isobutylene and water from methacrylic and acrylic estersto produce one or both of acid and anhydride functionalities, and may becatalyzed, e.g., acid-catalyzed. The thermally-induced reaction maycomprise the elimination of trialkylsilanes from trialkylsiloxy end orside group containing polymers to produce hydroxyl end or side groupfunctional polymers. The thermally-induced reaction may comprises theelimination of trialkylsilanes from trialkylsilazane end or side groupcontaining polymers to produce amino end or sidegroup functionalpolymers. The thermally-induced reaction may comprise a deesterificationreaction to produce hydroxyl- or carboxylic acid-functionalizedpolymers, and may be base-catalyzed. The thermally-induced reaction maycomprise the elimination of N₂ from acyl azides and subsequentrearrangement to form isocyanate functionality. The thermally-inducedreaction may comprise the elimination of benzenesulfenic acid frompoly(vinyl phenyl sulfoxide) to produce polyacetylene-containingpolymers. The thermally-induced reaction may comprise the elimination oftrialkylsilanes from trialkylsilthiane end or sidegroup containingpolymers to produce thiol end or side group functional polymers. Thethermally-induced reaction may comprise the elimination oftrialkylsilanes from trialkylsilyl-substituted ethynyl monomers, such as2-, 3- and 4-[(trimethylsilyl)-ethynyl]styrenes, producingethynyl-containing side-group or end functionalized polymers.

[0009] The mixing apparatus used to carry out the method may comprise ahigh viscosity devolatilizer or a devolatilizing kneader.

[0010] Another aspect of the invention is a composition of mattercomprising a controlled architecture material comprising at least onediene block and at least one (meth)acrylic anhydride block, andoptionally, at least one styrenic block. The composition may comprise ahydrogenated poly(diene-(meth)acrylic anhydride) controlled architecturematerial. The diene may be selected from the group consisting ofisoprene, butadiene, and cyclohexadiene.

[0011] Another aspect of the invention is a composition of mattercomprising a controlled architecture material comprising at least onestyrenic block and at least one block containingN-methylperfluorobutanesulfonamido. The composition may comprise apoly(styrenic-(meth)acrylicanhydride-2-(N-methylperfluorobutanesulfonamido) controlled architecturematerial. The composition may comprise a poly(styrenic-(meth)acrylicacid-2-(N-methylperfluorobutanesulfonamido) controlled architecturematerial.

[0012] Another aspect of the invention is a composition of mattercomprising a controlled architecture material comprising at least onediene block and at least one block containingN-methylperfluorobutanesulfonamido. The composition may further comprisea (meth)acrylic anhydride block and/or a (meth)acrylic acid block

[0013] Another aspect of the invention is a composition of mattercomprising a controlled architecture material comprising at least onediene block and at least one (meth)acrylic acid-co-(meth)acrylicanhydride block. The composition may optionally further at least onestyrenic block and/or at least one perfluoroalkyl (meth)acrylate blockcontaining at least one mer unit having the formula

[0014] where

represents a bond in a polymerizable or polymer chain; R_(f) is —C₆F₁₃,—C₄F₉, or —C₃F₇; R and R₂ are each independently hydrogen or alkyl of 1to 20 carbon atoms; n is an integer from 2 to 11; and x is an integer ofat least 1. 5 Another aspect of the invention is a composition of mattercomprising at least one styrenic block, at least one (meth)acrylicacid-co-(meth)acrylic anhydride block, and at least one perfluoroalkyl(meth)acrylate block containing at least one mer unit having the formula

[0015] where

represents a bond in a polymerizable or polymer chain; R_(f) is —C₆F₁₃,—C₄F₉, or —C₃F₇; R and R₂ are each independently hydrogen or alkyl of 1to 20 carbon atoms; n is an integer from 2 to 11; and x is an integer ofat least 1.

[0016] As used herein:

[0017] “block copolymer” means a polymer having at least twocompositionally discrete segments, e.g., a di-block copolymer, atri-block copolymer, a random block copolymer, and a star-branched blockcopolymer;

[0018] “continuous” means that reactants enter a reactor at the sametime (and, generally, at the same rate) that polymer product is exitingthe same reactor;

[0019] “devolatilizing kneader” means an apparatus that provides mixingor kneading action and is capable of operation under vacuum sufficientto remove volatile by-products;

[0020] “di-block copolymer” or “tri-block copolymer” means a polymer inwhich all the neighboring monomer units (except at the transition point)are of the same identity, e.g., -AB is a di-block copolymer comprised ofan A block and a B block that are compositionally different, ABA is atri-block copolymer in which the A blocks are compositionally the same,but different from the B block, and ABC is a tri-block copolymercomprised of A, B, and C blocks, each compositionally different;

[0021] “end functionalized” means a polymer chain terminated with asingle functional group on one or both chain ends;

[0022] “functional group” means an appended moiety capable of undergoinga reaction;

[0023] “high shear environment” means mixing conditions in whichphysical mixing elements provide shear stress and intense mixing toblend materials having high melt viscosities;

[0024] “high viscosity devolatilizer” means an apparatus that provides ahigh shear mixing environment and a vacuum sufficient to remove volatileby-products from a material or mixture of materials;

[0025] “hydrogenated” means fully or partially hydrogenated; i.e.,hydrogen has been added to all or some double bonds of an unsaturatedmolecule;

[0026] “in situ grafting” means a grafting reaction is carried out on amaterial that has been functionalized during the same process run; i.e.,the material is not removed from the reactor between the functionalizingand grafting reactions;

[0027] “living anionic polymerization” means, in general, a chainpolymerization that proceeds via an anionic mechanism without chaintermination or chain transfer. (For a more complete discussion of thistopic, see Anionic Polymerization Principles and Applications. H. L.Hsieh, R. P. Quirk, Marcel Dekker, NY, N.Y. 1996. Pg 72-127);

[0028] “living end” means a stable radical, cation, or anion capable ofundergoing further polymerization reactions;

[0029] “modify” means perform a reaction to change the chemical natureof a material or a mixture of materials by physical and/or chemicalreactions;

[0030] “plug” means a three dimensional slice of the reaction mixture;

[0031] “plug flow reactor (PFR)” means a reactor that ideally operateswithout axial mixing (see An Introduction to Chemical EngineeringKinetics and Reactor Design; Charles G. Hill, J. Wiley and Sons 1977, p.251) or shows no radial variation in concentration as materials areconsumed as they travel in the axial direction (see Elements of ChemicalReaction Engineering; H. Scott Fogler Prentice Hall, 1999.

[0032] “protected functional group” means a functional unit that isreactive after the removal of a “protective” group that preventsreaction at a particular site; “temperature-sensitive polymer” means apolymer susceptible to significant side reactions, such as degradation,or increased polydispersity index, as the reaction temperature rises;

[0033] “random block copolymer” means a copolymer having at least twodistinct blocks wherein at least one block comprises a randomarrangement of at least two types of monomer units;

[0034] “star-branched block polymer” or “hyper-branched block copolymer”means a polymer consisting of several linear block chains linkedtogether at one end of each chain by a single branch or junction point,also known as a radial block copolymer (See Anionic PolymerizationPrinciples and Applications. H. L. Hsieh, R. P. Quirk, Marcel Dekker,NY, N.Y. 1996. Pg 333-368);

[0035] “styrenic” means a styrene molecule with any type of substituent;

[0036] “temperature sensitive monomer” means a monomer susceptible tosignificant side reactions such as degradation, cross-linking, and chainscission with reactive sites, such as carbonyl groups, on the same, ordifferent, polymer chain as the reaction temperature rises; and

[0037] “thermally-induced reaction” means a reaction that is induced ordriven by heat.

[0038] An advantage of at least one embodiment of the present inventionis that functionalizations can be performed, solvent free, under milderconditions (i.e., at lower temperatures and for shorter times) than inbench-scale batch processes that lack appropriate mixing capability.This can provide significant economic and environmental advantages.

[0039] An advantage of at least one embodiment of the present inventionis that faster reaction times can be achieved for thermally-inducedreactions that produce volatile by-products, as compared to the samereactions carried out in a solution process (0.5-1 hour compared to 8hours). This is due to the ability to drive the reaction by drawing offthe volatile byproducts. An advantage of at least one embodiment of thepresent invention is that for anhydride formation, lower reactiontemperatures (120-150° C.) can be used than in the typical thermalprocesses (operated at 200-250° C.), such as extrusion or bench-scalebatch processes lacking high viscosity mixing capability. An advantageof at least one embodiment of the present invention is that it producesmaterials substantially free of by-products without the need forprecipitation or lengthy drying procedures.

[0040] An advantage of at least one embodiment of the present inventionis the ability to produce and process polymers having long chainscomprising deprotected groups and long chains of functionalizedmaterials. In solution modification processes, long polar or functionalgroup segments often show reduced solubility in solvents and showincreased viscosity due to hydrogen bonding considerations. Suchproblems are avoided in at least one embodiment of the present inventionbecause modifications are performed in a solvent-free environment.

[0041] An advantage of at least one embodiment of the present inventionis that the continuous nature of the process and ability to use theprocess in combination with other continuous processes results in a verycost-effective method for producing materials.

[0042] An advantage of at least one embodiment of the present inventionis that the process can be easily scaled-up to produce large quantitiesof product.

[0043] An advantage of at least one embodiment of the present inventionis that the process does not cause significant polymer degradation.

[0044] An advantage of at least one embodiment of the present inventionis that the extent of modification can be adjusted by varying the extentof thermal exposure, for example, by varying residence time. Forexample, the ratio of acid to anhydride moieties can be controlled inthe thermal modification of (meth)acrylic esters.

[0045] An advantage of at least one embodiment of the present inventionis that monomeric or oligomeric/polymeric amines and alcohols may beblended with suitable reactive or modifiable methacrylate estermaterials during thermal modification to produce transesterified orgrafted materials in one easy step. This can allow the synthesis of newand novel materials, not directly accessible by current synthesisroutes.

DETAILED DESCRIPTION

[0046] One aspect of the present invention employs thermally-inducedreactions to modify polymeric materials. Many types of thermally-inducedreactions are suitable for the present invention. One suitable type ofreaction is a rearrangement reaction in which the substituents ormoieties of a molecule are rearranged to form a new molecule, i.e., thebonding site of a substituent or moiety moves from one atom to anotherin the same molecule. Another suitable type of reaction is anelimination reaction in which one or more substituents is removed from amolecule. Specific types of reactions that can be carried out include,but are not limited to, pyrolysis reactions, acid-catalyzed reactions,deprotection reactions, condensation reactions, hydrolysis reactions,imidization reactions, base-catalyzed reactions, and deesterification,e.g., deacetylation. In a pyrolysis reaction, a complex molecule isbroken into simpler units by the use of heat. In an acid-catalyzedreaction, acid is used to drive or induce the thermal reaction. In adeprotection reaction, a protecting group is removed to expose areactive functional group. In a condensation reaction, two moleculesreact to form a new molecule and release a byproduct, which is typicallywater. In a hydrolysis reaction, water reacts with another molecule(e.g., ester) to form one or more new molecules. In an imidizationreaction, anhydrides react with primary amines via an intermediate amicacid functionality to form an imide ring and water. In a base-catalyzedreaction, base is used to drive or induce the thermal reaction. In adeesterification reaction, an ester is converted into a carboxylic acidor an anhydride. In a deacetylation reaction, an ester is converted intoan alcohol with removal of an acetyl group. See, for example, Hawker etal., Macromolecules, 1998, 31, 1024.

[0047] One type of reaction may be followed by a subsequent reaction.For example, the acid catalyzed desterification or modification reactionof poly(meth)acrylic esters to form polymethacrylic acid is followed bya condensation reaction to form polymethacylic anhydride or a functionalgroup exposed by a deprotection reaction may then be further reacted,e.g., by grafting a moiety to the deprotected site.

[0048] Once the initial reaction has occurred, further reactions, suchas hydrolysis, condensation and in situ grafting may be performed.

[0049] Reactor System

[0050] The thermally-induced reactions of the present invention arecarried out in a mixing apparatus that provides a high shear environmentand has devolatilization capabilities. The intensive mixing provided bya high shear environment continually brings different portions of thereacting mixture to the surface of the bulk of mixture material. At thebulk surface, reaction products are exposed to the vacuum in theapparatus. The vacuum causes the lower molecular weight products, whichare typically undesirable by-products, to be drawn out of the reactingmixture. Removal of the by-products causes the kinetics to favoradditional reactions. Accordingly, as the mixture moves through themixing apparatus, the desired (higher molecular weight) product iscontinuously produced, and remains in the mixture, while undesired (lowmolecular weight) by-products are removed from the mixture. The highshear and devolatilization characteristics of the apparatuses used inthe present invention, which provide a favorable reaction equilibrium,allow the thermally-induced reactions to be carried out at temperatureslower than would otherwise be required. The ability to use lowertemperatures provides the added advantage of enabling the production ofmolecules that could not be made previously due to problems with, e.g.,thermal degradation and crosslinking.

[0051] In the present invention, reactions are typically carried out attemperatures of about 100° C. to about 180° C. Many reactions that canbe carried out per the present invention normally require highertemperatures, e.g., 200° C. or higher because the apparatus used do notprovide efficient mixing and heat transfer. The higher temperatures areneeded to ensure that the inner portions of the bulk material aresufficiently heated to drive the reaction. However, these highertemperatures can have detrimental effects, such as polymer degradation,as explained above.

[0052] Even though the high shear environment and devolatilizationcharacteristics of the apparatus of the present invention allowreactions to be carried out at temperatures lower than would otherwisebe required, most of the processes are carried out at above-ambienttemperatures. When the polymer and/or the reaction mixture is processedat above-ambient temperatures, addition of a thermal stabilizer to thereaction mixture is preferred. A variety of thermal stabilizers,including hindered phenols and phosphites, are widely used in theindustry. Whichever stabilizer is used, it is preferably soluble in thereaction mixture and products; otherwise, a solvent will be necessary asa delivery mechanism.

[0053] The methods of the present invention can be carried out usingbatch or continuous processes. Methods of the present invention areparticularly advantageous for use with continuous systems such as thosedescribed in copending U.S. patent application Ser. No. 09/500,155,having the title “Continuous Process for the Production of ControlledArchitecture Materials,” because the apparatus of the present inventioncan be set up in series with a polymer-producing apparatus so that thestarting polymeric material is fed directly into the mixing apparatus.

[0054] The mixing apparatuses of the present invention are capable ofhandling highly viscous polymer melts. For example, they can processpolymer melts having viscosities as high as about 500,000 cps (500Pascal (Pa) seconds) and solids concentrations of about 1 to about 90weight %. They can process these high viscosity materials at residencetimes of about 10 to about 60 minutes. The mixing apparatuses also havedevolatilization capabilities. The apparatuses may come standard withvacuum equipment or may be fitted with vacuum equipment. The apparatusescan maintain a vacuum of about 1 to about 200 torr (about 133 to about26660 Pa) under high viscosity mixing conditions.

[0055] The mixing apparatus are also, preferably,temperature-controlled. The apparatuses may have one or moretemperature-controlled zones. If the apparatus has more than onetemperature-controlled zone, a temperature gradient can be maintainedthrough the mixing apparatus. This can be advantageous in manysituations, for example when carrying out an exothermic reaction,because the need for heat removal can vary throughout the reactor,depending on the reaction being carried out.

[0056] Apparatuses that are suitable for the present invention includehigh viscosity processors and vacuum-fitted high performance kneaders.These apparatuses provide a high shear environment, devolatilizationcapabilities, and, optionally, temperature-controlled zones.

[0057] A suitable high viscosity processor, which comes standard withvacuum equipment, is a LIST Discotherm B processor (available from ListAG, Acton, Mass.). The LIST Discotherm B high viscosity processor(described in more detail in the Examples section) is ideally suited foruse in the present invention. It provides intensive mixing and kneadingin combination with large heat-transfer surfaces and long residencetimes thereby enabling the reaction and the removal of by-products totake place with great ease. The heat transfer surfaces are continuouslyswept by kneading elements, which increases thermal efficiency andensures high heat transfer rates. The LIST's inner cavity also providesa large working volume (i.e., volume occupied by the reaction mixture)and fill level, thus allowing for high throughput and long retentiontimes. Also, the working volume occupies only about 60% of the totalvolume of the reactor, which provides ample room to allow fordisengagement and flashing of off-gases and vapors as they are broughtto the bulk surface by the intensive mixing.

[0058] Suitable kneaders, fitted with a vacuum system, include an MKD0,6-H 60 IKA kneader (described in more detail in the Examples section),Buss kneaders (available from Coperion Buss AG, Pratteln, Switzerland),and Srugo Sigma kneaders (available from Srugo Machines Engineering,Netivot, Israel). The kneaders are fitted with vacuum equipment byattaching a vacuum pump to vacuum ports on the kneader.

[0059] Process Variables

[0060] The production of desired modified polymers can be obtained bycontrolling various process variables. Process variables can influence,for example, the speed at which, and extent to which, a reaction takesplace, and ratio of functional groups produced. Variables that can bechanged when conducting the method include: concentration or compositionof starting material, type of starting material, pressure (i.e., vacuum)in the mixing apparatus, temperature and/or temperature profile in thereactor, type and amount of component or grafting agent added, degree ofmixing, residence time, and where and when additional components areintroduced into the high viscosity reactor. For example, the level ofdeprotection can be increased by increasing the temperatures and/orincreasing the vacuum levels to affectively remove byproducts. If lessdeprotection, modification or elimination is desired the vacuum levelcan be lessened or the temperature can be lowered.

[0061] The variables may be changed in a continuous manner or a stepwisemanner. The ability to control feed flows, feed locations, andcompositional variations in a high viscosity reactor provides anopportunity to produce a variety of compositions in a continuous,economical, and scalable fashion.

[0062] Starting Polymer Systems

[0063] Suitable starting polymeric materials include controlledarchitecture materials (CAM), which are polymers of varying topology(linear, branched, star, star-branched, combination network),composition (di-, tri-, and multi-block copolymer, random blockcopolymer, random copolymers, homopolymer, graft copolymer, tapered orgradient copolymer, star-branched homo-, random, and block copolymers),and/or functionality (end, site specific, telechelic, multifunctional,macromonomers).

[0064] The invention allows the modification of polymers synthesized bystep growth polymerizations, specifically tradition or living/controlledfree radical, group transfer, cationic or living anionicpolymerizations. Suitable starting polymers include the fluorinatedmaterials described in co-pending patent application U.S. Ser. No.______ [attorney docket number 57707US002], incorporated by reference.Of most industrially relevant are tradition or living/controlled freeradical and living anionic polymerizations.

[0065] The starting polymeric materials may be made by any method knownin the art. For example, the may be made by the method described incopending U.S. patent application Ser. No. 09/500,155.

[0066] The starting polymer systems may be synthesized in processes thatare carried out in batch, semibatch, continuous stirred tank reactor(CSTR), tubular reactors, stirred tubular reactors, plug flow reactors(PFR), temperature controlled stirred tubular reactors as described inWO 0158962 A1 and co-pending U.S. patent app. Ser. No. 09/824,330,static mixers, continuous loop reactor, extruders, shrouded extruders asdescribed in WO 9740929, and pouched reactors as described in WO 9607522and WO 9607674. The media in which the polymerizations may take placeare bulk, solution, suspension, emulsion, ionic liquids or supercriticalfluids, such as supercritical carbon dioxide.

[0067] Specific methods of making the starting polymer systems includeatom transfer radical polymerization (ATRP), reversibleaddition-fragmentation chain transfer polymerization (RAFT), andnitroxyl or nitroxide (Stable Free Radical (SFR) or persistantradical)-mediated polymerizations. These controlled processes alloperate by use of a dynamic equilibrium between growing radical speciesand various dormant species (see Controlled/Living RadicalPolymerization, Ed. K. Matyjaszewski, ACS Symposium Series 768, 2000).

[0068] Suitable starting materials include those with a terminalunsaturated carbon-carbon bond, such as anionically-polymerizablemonomers (see Hsieh et al., Anionic Polymerization: Principles andPractical Applications, Ch. 5, and 23 (Marcel Dekker, New York, 1996)and free radically-polymerizable monomers (Odian, Principles ofPolymerization, 3^(rd) Ed., Ch. 3 (Wiley-Interscience, New York, 1991.

[0069] At least one aspect of this invention provides utility inparticular for temperature-sensitive polymers. Examples of temperaturesensitive polymers include poly(styrenes), poly(dienes),poly((meth)acrylates), and mixtures thereof, as well as polymericsystems that degrade at elevated temperatures over long periods of time.

[0070] Other suitable monomers include those that have multiple reactionsites. For example some monomers may have at least twoanionically-polymerizable sites. This type of monomer will producebranched polymers. This type of monomer preferably comprises less than10 molar percent of a given reaction mixture because larger amounts tendto lead to a high degree of crosslinking in addition to branching.Another suitable monomer is one that has at least one functionality thatis not anionically-polymerizable in addition to at least one anionicallypolymerizable site.

[0071] Polyolefin-based CAM's are also suitable materials for themodification reactions of the present invention. These polyolefin CAM'smay be made by hydrogenation of polydiene systems. Particularly usefulare hydrogenated poly(butadiene), polyisoprene poly(1,3-pentadiene), andpoly(1,3-cyclohexadiene), which can be synthesized via “living” anionicpolymerization. Hydrogenation of such polydienes produces variouspolyolefins, the nature of which is controlled by the polymer backbonemicrostructure. For example hydrogenation of poly(1,4-butadiene)produces a polyethylene-like structure, while hydrogenation ofpoly(1,2-butadiene) produces a polyethylethylene (ie. polybutylene)structure.

[0072] This ability to hydrogenate and subsequently modifypolyolefin-based CAM's can be used to produce dispersants,compatibilizers, tie layers, and surface modifiers that are unique,polyolefin-miscible, and industrially-useful.

[0073] Hydrogenation of polymer blocks can be performed by variousroutes including homogeneous diimide reduction as described by Hahn inJ. Polym. Sci:Polym Chem. 1992, 30, 397, and by heterogeneous Pdcatalyzed reduction as described by Graessley J. Polym. Sci; Polym Phys.Ed., 1979, 17, 1211. The diimide reduction involves the use of organicreducing agents such as p-toluenesulfonhydrazide in the presence of atrialkyl amine (e.g., tripropyl amine) and xylene as a solvent attemperatures of 140° C.

[0074] Fluorinated materials, such as perfluorinated (meth)acrylates,are also suitable for use in the present invention. Fluorinated monomerunits may comprise co-monomers in the materials of the presentinvention. The fluorinated materials may comprise, for example, abackbone mer unit having the following Formula I

[0075] where

represents a bond in a polymerizable or polymer chain; R_(f) is —C₆F₁₃,—C₄F₉, or —C₃F₇; R and R₂ are each independently hydrogen or alkyl of 1to 20 carbon atoms; n is an integer from 2 to 11; and x is an integer ofat least 1. An example of a Formula I structure isN-methylperfluorobutanesulfonamido. The fluorinated materials may beend-functionalized at one or both terminus with reactive end groups. Ifthere are two reactive end groups, they may be the same or different.Fluorinated diene, methacrylate and styrenic homo and block copolymersend-functionalized with alcohol(s), thiol(s), and/or amine(s) may besynthesized anionically by the use of suitable anionic initiators whichcontain protected functional groups that can be removed by postpolymerization techniques. Suitable functional initiators are known inthe art and are described in, e.g., U.S. Pat. No. 6,197,891, U.S. Pat.No. 6,160,054, U.S. Pat. No. 6,221,991, and U.S. Pat. No. 6,184,338.

[0076] The fluorinated materials may be made by the same living anionicpolymerization methods previously described. A more detailed descriptionof some suitable fluorinated materials is in co-pending patentapplication U.S. Ser. No. ______ [Attorney Docket Number 57707US002].

[0077] Thermally-Induced Reactions

[0078] As previously stated, a variety of thermally-induced reactionsmay be carried out on starting materials using the processes of thepresent invention. This section provides non-limiting examples ofreactions that can be carried out.

[0079] One suitable reaction is the rearrangement of an acyl azide toprovide an isocyanate group (i.e., a Curtius rearrangement) as shown inFormula I

[0080] In this reaction N₂ is eliminated and a nitrogen atom replacesthe carbon atom that is attached to the polymer backbone to form anisocyanate functionality.

[0081] Various reactions may be carried out to produceacetylene-containing polymers. In these reactions, a sulfoxide ispyrolyzed to give the polyactylene and a sulfenic acid byproduct (RSOH)as shown in Formula II. For example, a benzenesulfenic acid may beeliminated from poly(phenyl vinyl sulfoxide)-containing copolymers toproduce polyacetylene-containing copolymers, such aspoly(styrene-acetylene) block copolymers. Polyacetylene is typicallydifficult to work with because it is very insoluble in other materials.However, including it in a block structure allows the final structure toremain soluble.

[0082] Vinyl sulfoxides having the general structure CH₂═CH—SOR aresuitable for polymerization. Applicable R groups include primary alkyl,aryl, and alkylaryl-amines, for example, an alkyl group having 1 to 10carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aralkylgroup having 7 to 22 carbon atoms or an aryl group having 6 to 12 carbonatoms.

[0083] In other suitable reactions, polymeric materials containingmethacrylic and acrylic esters can be modified, e.g., functionalized ordeesterified, by treatment with catalytic amounts of acid atabove-ambient temperatures. The treatment with acid at above-ambienttemperature causes ester alkyl-oxygen cleavage, resulting in the releaseof relatively volatile aliphatic reaction products to form (meth)acrylicacid functionalized polymers, followed by (in some cases) the release ofwater via a condensation reaction to form (meth)acrylic anhydridefunctionalized polymers as shown in Formula III. This method can beapplied to a vast array of polymeric reagents to produce acid andanhydride functionality.

[0084] Appropriate (meth)acrylic ester-containing polymers includehomopolymers, block copolymers, random copolymers, graft copolymers,starbranched and hyperbranched polymers. Specific examples include, butare not limited to, polymers containing t-butyl methacrylate, t-butylcrotonate, t-butyl acrylate, t-pentyl acrylate,1,1-dimethylethyl-α-propylacrylate,1-methyl-1-ethylpropyl-α-butylacrylate,1,1-dimethylbutyl-α-phenylacrylate, t-hexyl acrylate, t-octylmethacrylate, isopropyl methacrylate, cyclohexyl methacrylate, andt-pentyl methacrylate. The preferred systems include t-butyl acrylateand t-butyl methacrylate.

[0085] The reaction may also be carried out on block copolymerscontaining methacrylic or acrylic block segments. Block copolymerscontaining poly(methacrylic acid) (PMAA), poly(acrylic acid) (PAA),poly(methacrylic anhydride) and poly(acrylic anhydride) block segmentsare typically difficult to introduce into a polymeric material,particularly in block copolymer systems synthesized by anionic routes,due to the inability of methacrylic/acrylic acid or methacrylic/acrylicanhydride to participate in anionic polymerizations. The presentinvention makes it easier to introduce these groups because they are ina protected form, which is amenable to conventional livingpolymerization techniques. These protecting groups are readily removedusing the procedures described in this invention, resulting in a usefulstrategy to introduce these reactive functional groups into a polymericbackbone.

[0086] Polymeric materials containing t-butyl methacrylate groups areattractive reagents for this acid-catalyzed pyrolysis reaction becausethe t-butyl groups can be easily removed to produce methacrylic acid(PMAA) and methacrylic anhydride (PMAn) moieties, which may impart watersolubility or provide reactive functionality to polymer systems.

[0087] Suitable acids for the above modification or deesterificationinclude the aromatic sulfonic acids, methanesulfonic, ethanesulfonic,2-propanesulfonic, benzenesulfonic, trifluoromethanesulfonic, andpreferably, toluenesulfonic acid.

[0088] In addition to the catalytic acid modification, the methacrylateester functionality may also be modified by the use of an alkali metalsuperperoxide such as potassium superperoxide in a suitable solvent suchas a mixture of dimethyl sulfoxide and tetrahydrofuran. This techniquehas been taught for example by R. D. Allen, et al., CoulombicInteractions in Macromolecular Systems, A.C.S. Symposium Series, #302,pg. 79-92 (1986). The resulting modified product may be acidified withsmall amounts of an acid such as hydrogen chloride to improvesolubility. Due to the difficulty in handling such reagents, the lattermethod is not preferred for commercial use.

[0089] In processes other than those of the present invention,typically, t-butyl methacrylate segments undergo thermally induceddeesterification, under solventless conditions at temperatures above200° C., or in solution, in the presence of trace acid for extendedperiods (8-12 hr) at 110° C. These known processes have severaldrawbacks such as: (1) in the bulk state, anhydride formation ishampered by the inefficient removal of by-products such as water, whichcan be trapped due to hydrogen bonding with the newly formed methacrylicacid segments; and (2) solution deesterification of (meth)acrylatematerials often requires long reaction times, rendering any industrialsolution process costly.

[0090] At least one aspect of the present invention overcomes thesedrawbacks because it allows for a lower temperature solvent-freereaction and it provides superior mixing and vacuum control, which helpto drive the above equilibrium reaction to form materials with highanhydride levels.

[0091] In another aspect of this invention, polymeric materialscontaining styrenic-ester monomers can be modified by treatment with abase at above-ambient temperatures. Strong bases are known in the art.See, for example, Hawker et al., Macromolecules, 1998, 31, 1024.Examples include potassium t-butoxide and sodium t-butoxide and otheralkyl metal oxide bases, amines, metal alkyls known in the art. Inreactions of this sort, a molar equivalent of base is added to thereactor. Adding as little as ½ to 1 weight % of base will induce thedesired reaction. The treatment with base at above-ambient temperatureresults in cleavage and the release of relatively volatile aliphaticreaction products and the formation of the desired hydroxylfunctionalized polymers. For example the deesterification of estersproduces hydroxyl functionalized species, e.g., the deesterification ofpoly(4-acetoxystyrene) yields poly(4-hydroxystyrene). Deesterificationof esters can also lead to carboxylic functionalities, e.g., apoly(alkylbenzoate ester) can yield a poly(alkylbenzoic acid). FormulaIV shows a base-catalyzed deesterification.

[0092] For Formula IV, appropriate starting polymers include those thatcontain, for example, para-, meta-, or ortho-acetoxystyrene. R may beany alkyl ester or aryl ester, preferably a primary alkyl ester.

[0093] Aspects of the present invention are also suitable to carry outdeprotection reactions. Polymeric systems containing latent or protectedfunctional groups can be synthesized, for example, in an extruder orstirred tube reactor, or by other known methods. The protecting groupsare added to prevent the functional groups from reacting until thedesired stage of a reaction process. The functional groups can be sidegroups or end groups. They can be, e.g., ethylenically or acetylenicallyunsaturated. After being incorporated into a polymer, these protectedfunctional groups can undergo deprotection, to expose or producefunctionalities at desired locations in the polymeric material. Thefunctional groups will be in various locations in the backbone ifincluded in a random polymer; will be in segments of the backbone ifincluded in a block copolymer; and will be at the terminus of a polymerchain if included as a capping agent. An in situ formation of a blockcopolymer consisting of reaction of functionalized polymers and anotherpolymer bearing acceptable terminal groups is also possible duringreactive blending. Reaction of amines with anhydrides exhibitsufficiently fast kinetics in the melt state to provide technologicallyuseful, compatibilized polymer blends.

[0094] Diene, methacrylate and styrenic homo and block copolymersend-functionalized with alcohol(s), thiol(s), and/or amine(s) may besynthesized anionically by the use of suitable anionic initiators whichcontain protected functional groups that can be removed by postpolymerization techniques. Suitable functional initiators are known inthe art and are described in, e.g., U.S. Pat. No. 6,197,891, U.S. Pat.No. 6,160,054, U.S. Pat. No. 6,221,991, and U.S. Pat. No. 6,184,338.

[0095] End-functionalized materials can also be synthesized by addingreagents that contain reactive halogen or unsaturated groups capable ofquenching a “living” anionic polymerization as described above. Anionicpolymerizations are not readily amenable to the polymerization ofmonomers containing relatively acidic, proton-donating groups such asamino, hydroxyl, thiol, carboxyl or acetylene functional groups.However, these groups can be included in the polymer via incorporationin functional quenching agents, i.e., a reactive moiety containing aprotected functional group capable of quenching or terminating ananionically produced polymer chain, if protected by suitable protectinggroups that are stable at the conditions of anionic polymerization andcan be readily removed by post polymerization treatments. Suitablefunctional quenching agents include1,3-bis(trimethylsilyl)carbodiimmide, and1-(3-bromopropyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane.

[0096] Block copolymers containing hydroxyl, amino, or thiolfunctionalities are difficult to introduce into a polymeric material,particularly in systems synthesized by anionic routes, due to theinability of compounds such as hydroxyethyl methacrylate,4-vinylphenylethyl amines, or 4-vinylphenyl thiol to participate inanionic polymerizations. A popular route to these block copolymersinvolves the polymerization of (meth)acrylic- or styrenic-based monomershaving protected functional groups. After polymerization, a deprotectionreaction is carried out to produce hydroxyl, amine, and thiolfunctionalities. This method is an attractive approach to impartingwater solubility or providing reactive functionality to polymer systems.

[0097] Tert-alkyl-protected groups can also be removed by reaction ofthe polymer with para-toluenesulfonic acid, trifluoroacetic acid, ortrimethylsilyliodide to produce alcohol, amino, or thiolfunctionalities. Additional methods of deprotection of the tert-alkylprotecting groups can be found in T. W. Greene and P. G. M. Wuts,Protective Groups in Organic Synthesis, Second Edition, Wiley, New York,1991, page 41. Tert-butyldimethylsilyl protecting groups can be removedby treatment of the polymer with acid, such as hydrochloric acid, aceticacid, para-toluenesulfonic acid. Alternatively, a source of fluorideions, for instance tetra-n-butylammonium fluoride, potassium fluorideand 18-crown-6, or pyridine-hydrofluoric acid complex, can be employedfor deprotection of the tert-butyldimethylsilyl protecting groups.Additional methods of deprotection of the tert-butyldimethylsilylprotecting groups can be found in T. W. Greene and P. G. M. Wuts,Protective Groups in Organic Synthesis, Second Edition, Wiley, New York,1991, pages 80-83.

[0098] A number of trialkylsilane deprotection reactions are alsosuitable for the present invention. These reactions include acid andfluoride anion deprotection reactions that remove the protectingtrialkylsilane groups from terminal- or side-chain-functionalizedpolymers, such as trialkylsilthiane end- or side-group containingpolymers. For example, trialkylsilanes can then be removed by treatmentof the polymer with acid, such as hydrochloric acid, acetic acid,para-toluenesulfonic acid. Alternatively, a source of fluoride ions, forinstance tetra-n-butylammonium fluoride, potassium fluoride and18-crown-6, or pyridine-hydrofluoric acid complex, can be employed fordeprotection. Hydroxyl end- or side-group functionalized polymers, suchas that shown in Formula V, can be readily accessed by anionicpolymerization of styrene derivatives such as4-(t-butyldimethylsilyloxy)styrene, 5- or 4-vinyl-1,3-benzodioxoles and4-vinylphenyl ethanol protected with t-butyldimethylsilyl ortrimethylsilyl groups. Methacrylic hydroxyl-containing species can beaccessed by polymerization of 2-hydroxyethyl methacrylate protected witha trimethylsilyl group or 2,3-dihydroxypropyl methacrylate masked with adioxolane ring. The trimethylsilyl group or dioxolane ring can then beremoved.

[0099] Thiol end- or side-group functionalized polymers can be obtainedby the polymerization of 4-vinylphenyl thiol and 4-vinylphenylethylthiol protected with a t-butyldimethylsilyl group. Thet-butyldimethylsilyl group can then be removed.

[0100] Amino end- or side-group functionalized polymers can be obtainedby the polymerization of styrenic monomers derived from 4-vinylphenyl,4-vinylphenylmethyl, and 4-vinylphenylethyl amines protected with twotrimethylsilyl groups. The trimethylsilyl groups can then be removed.

[0101] Formyl (aldehyde) end- or side-group functionalized polymers canbe obtained by polymerizing styrenic systems derived fromdioxolane-functionalized benzaldehyde, andN-[(4-vinylphenyl)methylene]-cyclohexamine. 3,4-Acyl substitutedstyrenes can be incorporated by silyl enol ether routes such as thet-butyldimethylsilyl protected enol ethers of vinylacetophenones. Thet-butyldimethylsilyl groups can then be removed.

[0102] Carboxy end- or side-group functionalized polymers can beobtained by polymerizing 4-vinyl benzoic acid, protected with oxazoline,ester, or amido functionalities such as inN-(4-vinylbenzoyl)-N′methylpiperazine and t-butyl 4-vinylbenzoate.Methacrylate based trimethylsilyl methacrylate can also be employed. Theoxazoline, ester, or amido functionalities can then be removed bytreatment with acid.

[0103] Ethynyl (acetylene) side-group or end-functionalized polymers canbe obtained. For example, ethynyl can be introduced as part of apolymer's side chain structure through anionic polymerization of 2-, 3-and 4-[(trimethylsilyl)-ethynyl]styrenes. The trimethylsilane group(s)can then be removed.

[0104] Grafting

[0105] After materials have been deprotected such that a functionalgroup is exposed, subsequent reactions can be carried out immediately inthe apparatus of the invention. These subsequent reactions can includegrafting substituents onto the polymer backbone. Various graftingreactions may be carried out. Typically, these reactions could happen atroom temp but occur faster at higher temperatures.

[0106] The polymeric materials produced by acid-catalyzed pyrolysis ofmethacrylic and acrylic esters are methacrylic/acrylic acid ormethacrylic/acrylic anhydride functionalized polymers. These acid- andanhydride-functionalized polymers may participate in further graftingreactions including esterification, amidation, and imidizationreactions.

[0107] In the case of esterification, the acid- oranhydride-functionalized polymeric material is subjected to reactionwith small molecule nucleophiles, most preferably alcohols. Suitablealcohols that participate in this reaction consist of, but are notlimited to C₁ to C₂₀, that can contain one or a combination of alkyl,alkenyl, or alkynyl moieties, and which can be straight, branched, orcyclic, or a combination thereof. A lower aliphatic group is typicallyfrom C₁ to C₅. The term alkyl, as used herein, unless otherwisespecified, refers to a saturated straight, branched, or cyclic, primary,secondary, or tertiary hydrocarbon, preferably of C₁ to C₂₀. Mixtures ofthe foregoing aliphatic alcohols may also be employed. The preferredaryloxy groups (substituted or unsubstituted) may be derived fromaromatic alcohols including among others phenol; alkylphenols such ascresols, xylenols, p-, o-, and m-ethyl and propyl phenols and the like;halogen-substituted phenols such as p-, o-, and m-chloro and bromophenols and di- or tri-halogen substituted phenols and the like; andalkoxy-substituted phenols such as 4-methoxyphenol, 4-(n-butoxy) phenoland the like. Mixtures of the foregoing aromatic alcohols may also beemployed.

[0108] In the case of amidation or imidization, the acid- oranhydride-functionalized polymeric material is subjected to reactionwith amine nucleophiles. Suitable amines that participate in thisreaction consist of, but are not limited to, typically primary alkyl,aryl, and alkylaryl-amines. The primary amines formula is RNH₂ wherein Rstands for an alkyl group having 1 to 10 carbon atoms, a cycloalkylgroup having 5 to 12 carbon atoms, an aralkyl group having 7 to 22carbon atoms or an aryl group having 6 to 12 carbon atoms.

[0109] In addition to small molecule nucleophiles, polymericnucleophiles can be used to add functionality to polymer systems viagrafting reactions. For example, hydroxyl-terminated poly(lactide),poly(caprolactone), poly(dimethylsiloxane), and polyethylene glycol canbe synthesized by employing a protected alcohol as part of the catalystsystem, as known in the art. Amine terminated poly(lactide),poly(caprolactone), poly(dimethylsiloxane), polyethylene glycol, can besynthesized by employing a protected alcohol as part of the catalystsystem, as known in the art. Amine and alcohol terminated polymers canbe purchased from Aldrich (Milwaukee, Wis.), Tomah (Tomah, Wis.),Shearwater Polymers (Huntsville, Ala.), and Gelest (Morrisville, Pa.).

[0110] Diene, methacrylate and styrenic homo and block copolymersend-functionalized with alcohol(s), thiol(s), and/or amine(s) may besynthesized anionically by the use of suitable anionic initiators, whichcontain protected functional groups that can be removed by postpolymerization techniques. Suitable anionic initiators are known in theart and are described in, e.g., U.S. Pat. No. 6,197,891, U.S. Pat. No.6,160,054, U.S. Pat. No. 6,221,991, and U.S. Pat. No. 6,184,338.

EXAMPLES

[0111] Test Methods

[0112] Molecular Weight and Polydispersity

[0113] The average molecular weight and polydispersity of a sample wasdetermined by Gel Permeation Chromatography (GPC) analysis.Approximately 25 mg of a sample were dissolved in 10 milliliters (mL) oftetrahydrofuran (THF) to form a mixture. The mixture was filtered usinga 0.2 micron polytetrafluoroethylene (PTFE) syringe filter. Then about150 microliters (μL) of the filtered solution were injected into aPlgel-Mixed B column (available from PolymerLabs, Amherst, Mass.) thatwas part of a GPC system also having a Waters 717 Autosampler and aWaters 590 Pump (Waters Corporation, Milford, Mass.). The systemoperated at room temperature, with a THF eluent that moved at a flowrate of approximately 0.95 mL/min. An Erma ERC-7525A Refractive IndexDetector (JM Science, Grand Island, N.Y.) was used to detect changes inconcentration. Number average molecular weight (M_(n)) andpolydispersity index (PDI) calculations were based on a calibration modethat used narrow polydispersity polystyrene controls ranging inmolecular weight from 6×10⁶ to 600×10⁶. The actual calculations weremade with Caliber software (available from Polymer Labs, Amherst,Mass.).

[0114] Infared Spectroscopy

[0115] Samples were run by two methods: either by slicing small sliversof the sample with a scalpel and examining them on an IRiS Spectra-TechFourier Transform Infrared Microscope (available from ThermoSpectra-Tech, Shelton, Conn.) used in transmission mode or as smallslivers melt smeared onto CsBr or KBr crystals and run by transmissionon a Bomem MB-100 Fourier Transform Infrared Spectrometer (availablefrom ABB Bomen, Quebec City, Canada).

[0116] NMR Spectroscopy

[0117] The concentration of each block and confirmation of eliminationor rearrangement was determined by Nuclear Magnetic Resonance (NMR)spectroscopy analysis. A sample was dissolved in deuterated chloroformto a concentration of about 10 wt % and placed in a Unity 500 MHz NMRSpectrometer (available from Varian, Palo Alto, Calif.). Blockconcentrations were calculated from relative areas of characteristicblock component spectra. All spectra were with Hl NMR unless otherwiseindicated.

[0118] Diffusion Ordered Spectroscopy

[0119] NMR diffusion experiments were performed on a Varian INOVA 500MHz NMR spectrometer (Varian, Palo Alto, Calif.) using a NALORAC 5 mmdual broadband gradient probe. The samples were submitted for diffusionanalysis via DOSY (diffusion ordered spectroscopy) to determine ifcopolymerization and/or hydrolysis of t-butyl groups has occurred. ADOSY Bipolar Pulse Pair Stimulated Echo pulse sequence was used in thisexperiment, to permit separation of NMR signals in a mixture based onthe diffusion coefficients. The gradient was applied to the sample for50 msec before acquisition of the spectrum.

[0120] UV-Visible Spectroscopy

[0121] Spectra were run between a wavelength of 100 and 900 cm⁻¹ with aLambda 4B UV Vis Spectrophotometer (available from Perkin Elmer,Shelton, Conn.). Polymeric material, in the amount of from 1-3 mg, wasdissolved in 10 mL of dichloromethane. The resulting solution was placedin the spectrophotometer and an analysis was made.

[0122] Starting Polymeric Materials

[0123] Poly(isoprene-t-butyl methacrylate), (PI-t-BMA),poly(styrene-t-butyl methacrylate) (PS-t-BMA),poly(styrene-isoprene-t-butyl methacrylate) (PS-PI-t-BMA), andPFI2-endfunctionalized polystyrene ((t-butyldimethylsiloxy)propylterminated polystyrene) (PFI-2-PS), were synthesized by living anionicpolymerizations in a stirred, temperature controlled tubular reactor asdescribed in WO0158962, “Continuous Process for the Production ofControlled Architecture Materials”. PFI2-end functionalized polystyrene((t-butyldimethylsiloxy)propyl terminated polystyrene) (PFI-2-PS) wassynthesized by living anionic polymerizations in a stirred,temperature-controlled tubular reactor as described in WO0158962,“Continuous Process for the Production of Controlled ArchitectureMaterials” by the replacement of sec-butyl lithium with PFI-2 incyclohexane, available as 3-(t-butyldimethylsilyloxy)-1-propyllithiumfrom FMC-Lithium, Gastonia, N.C. Poly(styrene-vinylphenyl sulfoxide) wassynthesized by batch solution anionic polymerization as described byLeung et al. (Polymer 35, 1994, 1556). Poly(iso-octyl acrylateco-p-acetoxystyrene) and poly(iso-octyl acrylate-co-trimethylsilylacrylate) were synthesized under batch, solution conditions in xylene,by treatment of the monomer mixture with t-butyl peroxybenzoate(Aldrich) as the thermal initiator (2.5 wt % relative to monomer). Bothpoly(iso-octyl acrylate co-p-acetoxystyrene) and poly(iso-octylacrylate-co-trimethylsilyl acrylate) were 50% solids in o-xylene at apolymerization temperature of 120° C. Materials Description TolueneAvailable from Worum Chemical, St. Paul, Minnesota. IRGANOX 1076Octadecyl 3,5-di-tert-butyl-4 hydroxyhydro- cinnamate available fromCiba Specialty Chemicals Corp. Tarrytown, New York. p-Toluenesulfonicacid Available from Aldrich Chemical Co., monohydrate Milwaukee,Wisconsin. THF Tetrahydrofuran, available from ISP Technologies, Wayne,New York. Butylamine Available from Aldrich Chemical Co. OctylamineAvailable from Aldrich Chemical Co. Cyclohexylamine Available fromAldrich Chemical Co. 3-(Dimethylamino)- Available from Aldrich ChemicalCo. propylamine Cyclohexane Available from Worum Chemical. IsopreneAvailable from Aldrich Chemical Co. Styrene Available from AshlandChemical, Columbus, Ohio. t-Butyl methacrylate Available from SansEsters Corp., New York, New York. Diphenylethylene Available fromAcros/Fisher Scientific, Itasca, Illinois. sec-Butyl lithium An anionicinitiator, 1.3 Molar in cyclohexane, available from Aldrich Chemical Co.Vinyl phenyl sulfoxide Available from Aldrich Chemical Co. PFI-2 incyclohexane Available as 3-(t-butyldimethylsilyloxy)-1- propyllithium(PFI-2-PS) from FMC-Lithium, Gastonia, NC. Trimethylsilyl Available fromAldrich Chemical Co. methacrylate 4-Acetoxystyrene Available fromAldrich Chemical Co. Ethanolamine Available from Aldrich Chemical Co.Poly(ethylene glycol) Available at Mn 350 from Aldrich Chemical methylether Co. Iso-octyl acrylate Available from 3M Corporation, St. Paul,Minnesota. 2-(N-methylperfluoro Available from Available from 3M Corpo-butanesulfonamido)ethyl ration, St. Paul, Minnesota. methacrylate

[0124] Continuous Vacuum Reactor

[0125] Continuous synthesis reactions were performed in a high viscositydevolatilizer reactor (LIST Discotherm B6 High Viscosity Processor,available from List AG, Acton, Mass.). The reactor, having a totallength of about 13.8 cm and an inside diameter of 2.8 cm consisted of ahorizontal, cylindrical housing, comprising 3 zones. Located in thecenter of the housing was a concentric main screw agitator shaft, havinga diameter of about 6.35 cm. Mounted on the shaft (and extendingperpendicular to the shaft) were disk elements that had angledperipheral mixing-kneading bars (extending generally parallel to theshaft). Stationary hook-shaped bars mounted on the inside of the housinginteracted with and cleaned the shaft and disk elements as they rotated.The arrangement of the disk elements and mixing-kneading bars in concertwith the stationary hook-shaped bars imparted a substantially forwardplug-flow movement to the material with minimal axial intermixing. (Theplug flow nature of the reactor was quantified by using a dough-likeproduct injected with a tracer to obtain a residence time distributioncurve. The curve was plotted against a theoretical curve for 14 idealcontinuous stirred tank reactors in series. The data fit the theoreticalcurve well, indicating plug-flow behavior.) Material was discharged fromthe LIST by a twin-screw discharge screw.

[0126] The total volume in the reactor was 17.5 L, with a working volumeof 12L. The housing, shaft, and disk elements were all heated via a hotoil heating system. The heat transfer area in the reactor was 0.67 m².Temperature was controlled and monitored in three locations within thereactor: (1) the reactor entrance zone (temperature Ti), (2) the reactorintermediate zone (temperature T2) and (3) the reactor exit zone(temperature T3). A variable speed motor drove the agitator shaft atspeeds of 5 to 70 rpm and a maximum torque of 885 ft lbs (1200 Nm). Avacuum pump was attached to the reactor for vapor removal. Thecondensate was collected in two evacuated, high vacuum glass solventtraps, which were submersed in a slurry bath consisting of a suitablecoolant, typically ISOPAR((isoparaffin hydrocarbons C₁₈₋₂₅) availablefrom Exxon Company USA, Houston, Tex.) and dry ice (CO₂).

[0127] Batch Vacuum Reactor

[0128] Batch synthesis reactions were performed in a high performancemeasuring kneader, the MKD 0,6-H60 IKAVISC Measuring Kneader (availablefrom IKA Labortechnik, Janke & Kunkel Gmbh & Co. KG, Germany). Thekneader consisted of a kneading trough that held 600 ml and had aworking volume of 300 ml. The bottom of the trough was double walledallowing the batch to be heated via a hot oil circulator. Kneading wasaccomplished with two kneading paddles, which were fixed to the motor,that mix the polymeric materials both horizontally and vertically. Thepaddles continually wiped the walls and each other. In the lid was aport from which a vacuum could be established and liquid could beintroduced.

[0129] The speed of the kneader paddles was controlled with an RE 162/PAnalog Controller (available from IKA Labortechnik). The speed of thepaddles could range from 0.5 to 64 rpm. Torque was measured with a ViseMS Torque Meter (available from IKA Labortechnik). Temperature wasmeasured from within a paddle with an Ikatron DTM11 thermometer,(available from IKA Labortechnik). Vacuum was measured digitally with a375 Convection Vacuum Meter (available from Greenville Phillips,Boulder, Colo.). A DC motor with a constant power output of 160 W wasmounted downstream from a gear assembly that was capable of transmittinga torque of 60 Nm to drive the paddles. The kneader was heated by anEXOCAL EX-250 HT High Temperature Bath equipped with a High TemperatureBath Controller/Readout having a temperature range of 40° C. to 250° C.(both available from Neslab, Portsmouth, N.H.). A heat transfer fluid (aC₁₁ to C₂₅ petroleum hydrocarbon, available as STEFRIFLUSH, fromPetro-Canada, Calgary Alberta, Canada) was used in the bath. Vacuum wassupplied, for vapor removal, via a double stage rotary vacuum pump(Model RV5 vacuum pump with a 4.1 cfm (117L/min) displacement, ultimatevacuum (without gas ballast) of 1.5×10⁻³ torr (200 mPa), maximum inletpressure for water vapor of 38 torr (5.1 kPa), and a ½ hp (0.373 kW)motor, available from Boc Edwards, Wilmington, Mass.). Condensate wascollected in two evacuated, high vacuum glass solvent traps, which weresubmersed in Dewars flasks containing liquid nitrogen.

Example 1 Batch Synthesis of poly(isoprene-methacrylic acid/anhydride)via the p-toluenesulfonic Acid Catalyzed Modification ofpoly(isoprene-t-butyl methacrylate) and Subsequent Transesterificationwith poly(ethylene glycol) Methyl Ether.

[0130] This example illustrates that this invention may be used tomodify temperature sensitive polymer systems, such as polyisoprene,which undergo crosslinking reactions upon extended exposure to hightemperatures (>100° C.). Additionally, this example shows the ability toperform grafting reactions from the acid and anhydride materials formedin-situ.

[0131] A solution of poly(isoprene-t-butyl methacrylate) (PI-t-BMA) intoluene, 250 grams at a concentration of 60 wt % solids, was siphonedinto the batch vacuum reactor set at 100° C. and agitated at a speed of68 rpm to create a torque of 11 Nm. A vacuum of about 1170 Pa (8.8 torr)was applied for 30 minutes to evaporate the solvent. The temperature ofthe reactor was increased to 106° C., a solution of p-toluenesulfonicacid monohydrate in THF, 20 g at 13 wt % solids, was siphoned into thereactor, and the internal vacuum of the reactor was re-established atabout 1170 Pa. After 30 minutes, the color of the modified startingmaterial, PI-t-BMA, had changed from white to light yellow, and themeasured torque had increased to 13 Nm. Then 12.2 g of the nucleophilepoly(ethylene glycol) methyl ether (PEGME) was siphoned into the reactoras a neat liquid and the internal vacuum of the reactor wasre-established to 1200 Pa (9.0 torr). The contents were removed after 15minutes.

[0132] Samples were tested with Infrared Spectroscopy, NMR Spectroscopyand Diffusion Ordered Spectroscopy. Results from Infrared Spectroscopyconfirmed that modification had occurred. The spectra illustrated IRresonances indicative of the formation of anhydride functionalities(1801 and 1760 cm⁻¹), an ester carbonyl, indicating the presence of amethacrylate moiety (1734 cm⁻¹), and an acid functionality (the shoulderpeak at 1709 cm⁻¹). Results of NMR Spectroscopy confirmed the loss oft-butyl methacrylate groups and the presence of grafting of PEGME. Theresults for Example 1 are depicted in Table 1 following Example 4.Results of Diffusion Ordered Spectroscopy revealed that the PEGME hadgrafted and that the reaction mixture consisted of a mixture ofhydrolyzed PI-t-BMA and the copolymer with PEGME grafted thereon.

Example 2 Batch Synthesis of poly(styrene-methacrylic acid/anhydride)via the p-toluenesulfonic Acid Catalyzed Modification ofpoly(styrene-t-butyl methacrylate) and Subsequent Grafting with Amines.

[0133] This example illustrates that this invention may be used to graftmixtures of nucleophiles onto acid and anhydride functionalities formedin-situ.

[0134] A solution of poly(styrene-t-butyl methacrylate) (PS-t-BMA) incyclohexane, 300 g at a solids concentration of 40 wt %, followed by asolution of Irganox 1076 in THF, 24 g at a solids concentration of 17 wt%, were siphoned into the batch vacuum reactor set to a temperature ofabout 100° C. The solutions were mixed at a speed of 68 rpm under atorque of 30 Nm. Solvents were evaporated from the reaction mixture byapplying a vacuum of about 667 Pa (5.0 torr) to the reactor andagitating the mixture for 30 minutes. The batch temperature of thereactor was increased to 140° C. at which point, 4 g p-toluenesulfonicacid monohydrate was added into the reactor and the internal vacuum ofthe reactor was re-established to about 667 Pa. After mixing for anadditional 15 minutes, the color of the modified starting PS-t-BMAmaterial had changed from white to dark brown. The reaction mixture wassampled at this point.

[0135] The intermediate sample was tested with Infrared Spectroscopy.The resulting spectra depicted characteristic IR spectra indicative ofthe formation of anhydride (IR bands at 1801 and a shoulder peak at 1760cm⁻¹), an ester carbonyl indicating the presence of a methacrylatemoiety (the 1734 cm⁻¹ band) and an acid functionality (a band at 1709cm⁻¹).

[0136] Octylamine, in an amount of 5 g, was siphoned into the reactionmixture and the internal vacuum of the reactor was re-established toabout 667 Pa. Butyl amine, in an amount of 15 g, was siphoned into thereactor after about 5 minutes and the internal vacuum of the reactor wasre-established to about 667 Pa. The contents were removed after 5minutes.

[0137] The final sample was tested with Infrared Spectroscopy, NMRSpectroscopy, and Diffusion Ordered Spectroscopy. Results from InfraredSpectroscopy confirmed that modification and the formation of anhydride,acid, and grafted amide occurred. The spectra illustrated IR resonancesindicative of the formation of methacrylic anhydride (IR bands at 1801and a shoulder peak at 1760 cm⁻¹), ester (1734 cm⁻¹), acid (1709 cm⁻¹),and amide (1644 cm⁻¹). Results of NMR Spectroscopy confirmed the loss oft-butyl methacrylate groups. The results for Example 2 are depicted inTable 1 following Example 4. Results from Diffusion Ordered Spectroscopyconfirmed the loss of the t-butyl group from the copolymer.

Example 3 Batch Synthesis of poly(isoprene-methacrylic acid) via thep-toluenesulfonic Acid Catalyzed Modification of poly(isoprene-t-butylmethacrylate).

[0138] This example illustrates that i) this invention may be used tomodify temperature sensitive polymer systems, such as polyisoprene,which undergo crosslinking reactions upon extended exposure to hightemperatures (>100° C.) and ii) by controlling reaction time in thereactor, acid functionality can be preferentially produced at shortreaction times.

[0139] A solution of poly(isoprene-t-butyl methacrylate) (PI-t-BMA) intoluene, 365 g at a solids concentration of 60 wt %, was siphoned intothe batch vacuum reactor set at a temperature of 100° C. and agitated ata speed of 68 rpm with a torque of 16 Nm. The solvent was evaporatedfrom the solution by applying a vacuum of about 467 Pa (3.5 torr) to thereactor and agitating the solution for about 20 minutes. The temperatureof the reactor was increased to 111° C., p-toluenesulfonic acidmonohydrate in the amount of 1.5 g was added into the reactor and theinternal vacuum of the reactor was re-established to about 467 Pa. After10 minutes, the color of the modified starting PI-t-BMA material hadchanged from white to light yellow, and the torque, measured with atorque meter, had increased to 17 Nm, indicating a viscosity increase.

[0140] The reaction product was tested with Infrared Spectroscopy andNMR Spectroscopy. Results of Infrared Spectroscopy confirmed thatmodification had occurred and that acid was formed. The spectraillustrated IR resonances indicative of the presence of methacrylic acid(1712 cm⁻¹ associated with an acid functionality). Results of NMRSpectroscopy confirmed the loss of t-butyl methacrylate groups. Theresults for Example 3 are depicted in Table 1 following Example 4.

Example 4 Batch Synthesis of poly(styrene-isoprene-methacrylicacid/anhydride) via the p-toluenesulfonic Acid Catalyzed Modification ofpoly(styrene-isoprene-t-butyl methacrylate) and Subsequent Grafting withAmines.

[0141] This example illustrates a reaction with another class ofpolymers, that of an ABC triblock copolymer.

[0142] A solution of poly(styrene-isoprene-t-butyl methacrylate)(P(S-1-t-BMA)) in cyclohexane, 337 g at a solids concentration of 40 wt%, was siphoned into the batch vacuum reactor set at 100° C. and mixedat a speed of 68 rpm with a torque of 13 Nm. The solvent was evaporatedfrom the solution by applying a vacuum to the reactor at 467 Pa (3.5torr) over the next 30 minutes. The temperature of the reactor wasincreased to 133° C. and both 1 g of Irganox 1076 and 1.5 g ofp-toluenesulfonic acid monohydrate were added into the reactor. Theinternal vacuum of the reactor was re-established to about 467 Pa. After10 minutes, the color of the modified starting P(S-1-t-BMA) material hadchanged from white to light yellow. The reaction mixture was sampled.

[0143] The sample was tested with Infrared Spectroscopy and NMRSpectroscopy. Results of Infrared Spectroscopy revealed the presence ofresonances attributable to anhydride and acid. The spectra depicted IRbands at 1802 and 1760 cm⁻¹ which are associated with an anhydride, aband at 1734 cm⁻¹ associated with an ester carbonyl, indicating thepresence of a methacrylate moiety, and a shoulder peak at 1706 cm⁻¹associated with an acid functionality. Results of NMR Spectroscopyconfirmed the loss of t-butyl methacrylate groups. The results forExample 4 are depicted in Table 1 together with those of Example 1-3.TABLE 1 t-BMA mole % Temp. Graft Time Example Starting Material beforeafter ° C. Nucleophile (min) 1 PI-t-BMA 30.9 7.1 106 poly(ethyleneglycol) 15 methyl ether (PEGME) 2 PS-t-BMA 24 1.0 132 octylamine 30 3PI-t-BMA 30.9 1.7 130 none na 4 PS-PI-t-BMA 23.5 2.0 133 none na

Example 5 Batch Synthesis of poly(styrene-acetylene) Block Copolymersvia the Thermal Modification of poly(styrene-vinyl phenyl sulfoxide).

[0144] This example illustrates the thermal elimination ofbenzenesulfenic acid from poly(styrene-vinyl phenyl sulfoxide)(P(S-VPS)) to produce a poly(styrene-acetylene) block copolymer.

[0145] A solution of (P(S-VPS)) in toluene, 200 g at a solidsconcentration of 57 wt %, was siphoned into the batch vacuum reactor setto 100° C. and mixed at a speed of 68 RPM with a torque of 16 Nm. Thesolvent was evaporated from the solution by applying a vacuum of about400 Pa (3.0 torr) to the reactor over the next 30 minutes. After 30minutes, the color of the modified starting P(S-VPS) material hadchanged from light yellow to burgundy red. The reaction mixture wassampled and the contents of the reactor were removed.

[0146] The sample was tested with NMR Spectroscopy and UV-VisibleSpectroscopy. The results of NMR Spectroscopy confirmed the loss ofbenzenesulfenic acid. The results of UV-Visible Spectroscopy confirmedthe presence of resonances attributable to polyacetylene chromophores(bands between 375 and 500 nm).

Example 6 Deprotection of PFI-2-End-Functionalized Polystyrene((t-butyldimethylsiloxy)propyl Terminated Polystyrene) (PFI-2-PS)

[0147] This example illustrates deprotection reactions resulting in theformation of reactive, end-functional materials.

[0148] A mixture of a solution of PFI-2-PS in cyclohexane, 364 g at asolids concentration of 40 wt %, and 1 g of Irganox 1076 was siphonedinto the batch vacuum reactor set at 100° C. and agitated at a speed of68 rpm with a torque of 24 Nm. The solvent was evaporated from thesolution by applying a vacuum at 3.3 kPa (25 torr) to the reactor for 30minutes. The temperature of the reactor was increased to 122° C., 1.5 gof p-toluenesulfonic acid monohydrate was added, and the internal vacuumof the reactor was re-established to about 3.3 kPa. After 30 minutes,the color of the modified starting PFI-2-PS material had changed fromwhite to light brown. The reaction mixture was sampled after 30 minutesand the contents of the reactor were removed.

[0149] Samples were tested with NMR Spectroscopy and Diffusion OrderedSpectroscopy. Results form NMR Spectroscopy confirmed the loss oft-butyl(dimethyl)silyl (t-BuSi) groups associated with the PFI-2 endgroup. Results from Diffusion Ordered Spectroscopy showed that nopolymeric PFI-2-functionalized polystyrene was present, but that freet-Bu(Me)₂Si groups and polystyrene were present. This indicates that allof the protecting groups were removed, but not all were devolatilized.Quantitative results (in mole % and wt %) are shown in Table 2. TABLE 2Free t-Bu(Me)₂Si Example mole % poly t-Bu(Me)₂Si mole % PS mole % 6 0.10.0 99.9

Example 7 Batch Synthesis of poly(iso-octylacrylate-co-p-hydroxystyrene) via Base Catalyzed Modification ofpoly(iso-octyl acrylate-co-p-acetoxystyrene)

[0150] This example illustrates the production of functional styrenicmaterials, via the base catalyzed hydrolysis of the random copolymer ofpoly(iso-octyl acrylate-co-p-hydroxystyrene), which serves as aprecursor to poly(p-hydroxystyrene) segments.

[0151] A mixture of a solution of poly(iso-octylacrylate-co-p-acetoxystyrene) in xylene, 360 g at a solids concentrationof 50 wt %, and 1 g of Irganox 1076, was siphoned into the batch vacuumreactor set at 120° C. and agitated at a speed of 68 rpm with a torqueof 24 Nm. The solvent was evaporated from the solution by increasing thetemperature to 140° C. and applying a vacuum of 3.3 kPa (25 torr) to thereactor for 40 minutes. Sodium t-butoxide (NaOt-Bu) in an amount of 1.5g was added and the internal vacuum of the reactor was re-established to3.3 kPa. After 30 minutes, the color of the modified starting polymericmaterial had changed from white to light brown and the reaction mixturewas sampled. Similar sampling was performed 30 minutes after thetemperature had been raised to 150° C. and again 30 minutes after thetemperature had been raised to 160° C.

[0152] Each sample was tested with NMR Spectroscopy. Results confirm aloss of acetic acid and a diminished mole % of acetoxystyrene.Quantitative results are shown in Table 3. TABLE 3 Sample DescriptionP(IOA) P(acetoxystyrene) 7A P(IOA/4-acetoxystyrene) Starting 53.3% 46.4%Material 7B P(IOA/4-acetoxystyrene) + 97.8% 2.2% NaOt-Bu at 140° C. 7CP(IOA/4-acetoxystyrene) + 98.7% 1.3% NaOt-Bu at 150° C. 7DP(IOA/4-acetoxystyrene) + 98.7% 1.3% NaOt-Bu at 160° C.

Example 8 Batch Synthesis of poly(iso-octyl acrylate-co-trimethylsilylmethacrylate) via the Acid Catalyzed Modification of poly(iso-octylacrylate-co-trimethylsilyl Methacrylate).

[0153] This example illustrates the production of side-chainacid-functional materials, via the acid catalyzed modification of therandom copolymer of poly(iso-octyl acrylate-co-trimethylsilylmethacrylate).

[0154] A mixture of a solution of poly(iso-octylacrylate-co-trimethylsilyl methacrylate) in xylene, 360 g at a solidsconcentration of 50 wt %, and 1 g of Irganox 1076, was siphoned into thebatch vacuum reactor set at 120° C. and agitated at a speed of 68 rpmwith a torque of 24 Nm. The temperature was increased to 140° C. and thesolvent was removed by applying a vacuum of 2.2 kPa (25 torr) to thereactor for 40 minutes. P-toluenesulfonic acid monohydrate in an amountof 1.5 g was added into the reactor and the internal vacuum of thereactor was re-established to 3.3 kPa. After 30 minutes, the color ofthe modified starting polymeric material had changed from white to lightbrown and the reaction mixture was sampled. The temperature was raisedto 150° C. and another sample was taken after an additional 30 minuteshad elapsed.

[0155] Samples were tested with Infrared Spectroscopy and NMRSpectroscopy. Results of Infrared Spectroscopy revealed the presence ofbands at 1707 cm⁻¹ corresponding to carboxylic acid groups. Results ofNMR Spectroscopy confirmed the presence of methacrylic acid.Quantitative results are given in Table 4. TABLE 4 P(methacrylic acid)Example Description mole % 8A Poly(iso-octyl acrylate-co-trimethylsilyl0.0% methacrylate) 8B Poly(iso-octyl acrylate-co-trimethylsilyl 9.3%methacrylate) + PTSA at 140° C. 8C Poly(iso-octylacrylate-co-trimethylsilyl 9.2% methacrylate) + PTSA at 150° C.

Example 9 Continuous Synthesis of poly(styrene-methacrylicacid/anhydride) via the p-toluenesulfonic Acid Catalyzed Modification ofpoly(styrene-t-butyl methacrylate).

[0156] This example illustrates a continuous, scaleable process that canbe combined with other continuous reactor technology (in this case atemperature-controlled, stirred tubular reactor) and the lowertemperatures that can be used for the modification reaction by employinga continuous operation.

[0157] A solution of PS-t-BMA in toluene was made in a stirred tubularreactor (STR) according to WO0158962, “Continuous Process for theProduction of Controlled Architecture Materials”, Example 6, at a solidsconcentration of about 37 wt %. The block copolymer composition variedin both number average molecular weight and polydispersity index as afunction of time from start-up as shown in Table 5. This shows theinitial t-butyl methacrylate levels.

[0158] A solution of p-toluenesulfonic acid monohydrate in toluene wasprepared by mixing 463 g of p-toluenesulfonic acid monohydrate in 4169 gtoluene. The p-toluenesulfonic acid monohydrate catalyst solution waspumped via peristaltic pump at a rate of 9.6 g/min into the last zone ofthe STR and mixed with the PS-t-BMA solution in a ratio of 0.0083 to 1.TABLE 5 Time Styrene t-BMA M_(n) Example min mole % mole % ×10⁴ PDI 9A 0 92.8  7.2 2.59 2.43 9B 13 80.3 19.7 3.26 2.48 9C 60 76.7 23.3 3.122.68

[0159] The resultant solution was pumped (via a zenith pump at 19.7 rpm)from the STR to the first zone of the Continuous Vacuum Reactor. Thespeed of the main screw agitator shaft of the vacuum reactor was keptconstant at approximately 34 rpm, while the discharge screw of thereactor was maintained at 47 rpm. The reactor was maintained at a vacuumof about 2.7 kPa (20 torr) and at temperatures of between 150-175° C.

[0160] The resulting material was tested with Infrared Spectroscopy andNMR Spectroscopy. Results of the Infrared Spectroscopy confirmed thepresence of anhydride groups (1760 cm⁻¹). The reactor was sampled atvarious intervals. All of the samples showed the presence of anhydride.Quantitative results shown in Table 6 include a comparison of the areaunder an Infrared Spectroscopy spectra band at 1760 cm⁻¹ (from theanhydride) to the area under a spectra band at 1601 cm⁻¹ (an aromaticring absorption) The aromatic absorption should remain constant as it isassociated with the PS block. —This allows tracking of changes in theanhydride level. Time 0 indicates when the first sample was taken. TABLE6 Time PS Pt-BMA M_(n) Area Area Ratio of Areas Example min mole % mole% ×10⁴ PDI 1601 cm⁻¹ 1760 cm⁻¹ 1760/1601 cm⁻¹ 9D 0 95.9 4.1 2.29 2.210.65 0.65 1 9E 30 97.8 2.2 2.28 2.18 0.54 0.59 1.09 9F 35 98.7 1.3 2.372.13 1.02 1.24 1.22 9G 105 99.2 0.8 2.51 2.13 1.48 1.6 1.08 9H 150 99.10.9 2.45 2.21 0.65 0.79 1.22

[0161] Results of NMR Spectroscopy revealed the revealed the significantreduction of the t-butyl groups, consistent with hydrolysis.

Example 10 Continuous Synthesis of poly(isoprene-methacrylicacid/anhydride) via the p-toluenesulfonic Acid Catalyzed Modification ofpoly(isoprene-t-butyl methacrylate).

[0162] This example illustrates a synthesis reaction using temperaturesensitive materials that are susceptible to crosslinking at elevatedtemperatures, and the ability to control the acid to anhydride ratio byvarying temperature in the Continuous Vacuum Reactor.

[0163] Example 10 was made in a manner similar to Example 9 exceptdifferent materials were used and some conditions were changed.P-Toluenesulfonic acid monohydrate in the amount of 76 g was added to asolution of poly(isoprene-t-butyl methacrylate) in toluene (19 kg atsolids concentration of 40 wt %) in a wt ratio of p-toluenesulfonic acidmonohydrate to poly(isoprene-t-butyl methacrylate) solution of 1:100.The mixture was agitated with an air-powered stirrer operating at 100rpm at room temperature for 20 minutes. The resultant solution waspumped (via a Zenith pump at 19.7 rpm) to the first zone of thecontinuous reactor. The temperature settings in the reactor were variedto explore the effect of temperature on extent of hydrolysis andcrosslinking. Temperatures that were varied were (1) the reactorentrance zone temperature (T1), (2) the reactor intermediate zonetemperature (T2) and (3) the reactor exit zone temperature (T3). Table 7indicates the temperature settings and resulting vacuum readings.

[0164] Samples were tested continuously with Infrared Spectroscopy. Thecontinuous process was stopped when crosslinking was observed. Thecontinuous run was started again when the temperature decreased to arange at which crosslinking would not occur.

[0165] Results of Infrared Spectroscopy revealed the presence ofcharacteristic bands at 1801 and 1758 cm⁻¹ associated with an anhydride,at 1709 cm⁻¹ associated with an acid functionality and at 1736 cm⁻¹associated with an ester carbonyl as in a methacrylate moiety. The ratioof the anhydride to the acid and the ratio of the ester to the acid wascalculated from areas under various bands of the infrared spectra. Theratios are also shown in Table 7. TABLE 7 Time T1 T2 T3 Vacuum Ratio ofRatio of Example min ° C. ° C. ° C. kPa (Torr) Anhydride:Acid Ester:Acid10A 0 91 100 103 19.2 (144) 0.08 0.73 10B 10 91 100 110 19.2 (144) 0.100.72 10C 25 99 110 116 18.0 (135) 0.16 0.75 10D 32 104 112 124 17.6(132) 0.29 0.83 10E 56 113 120 136 16.9 (127) Crosslinked Crosslinked10F 295 88 100 113 16.0 (120) 0.49 0.90 10G 305 88 100 113 16.0 (120)0.30 0.91 10H 315 88 100 113 16.0 (120) 0.33 0.91 10I 325 88 100 10216.0 (120) 0.14 0.75

Example 11 Batch Synthesis ofpoly(2-(N-methylperfluorobutanesulfonamido)ethylmethacrylate)-b-methacrylic anhydride/acid) via the p-toluenesulfonicacid Catalyzed Hydrolysis of Poly(2-(N-methylperfluorobutanesulfonamido)Ethyl Methacrylate-t-butyl Methacrylate) (P(MeFBSEMA-t-BMA)).

[0166] This example illustrates hydrolyzing semifluorinated blockcopolymer systems, such as poly(2-(N-methylperfluorobutanesulfonamido)ethyl methacrylate-t-butyl methacrylate) (P(MeFBSEMA-t-BMA)).

[0167] Starting materials were prepared in the following manner:

[0168] Reactant monomers t-butyl methacrylate (t-BMA), MeFBSEMA(2-(N-methylperfluorobutanesulfonamido) ethyl methacrylate), and1,1′diphenylethylene in cyclohexane were nitrogen sparged until the O₂concentration was less than 1 part per million (ppm).

[0169] Reaction solvents (cyclohexane, THF) were pumped throughmolecular sieve beads (available as Zeolite 3A from UOP, Chickasaw,Ala.).

[0170] An initiator slurry was prepared by mixing 50 g of 1.3 Msec-butyl lithium solution with 600 g of dry, oxygen-free cyclohexaneand slowly adding 16.8 g of deoxygenated 1,1′-diphenylethylene withstirring at room temperature, resulting in the formation of1,1′-diphenylhexyllithium.

[0171] Deoxygenated MeFBSEMA monomer was purified by recrystallizationfrom hot toluene, washed with anhydrous heptane, and dried overnight atroom temperature in a vacuum oven. The purified MeFBSEMA monomer (400 g)was then diluted with 2000 g of toluene to form a solution having asolids concentration of about 20 wt %.

[0172] Deoxygenated t-butyl methacrylate monomer was pumped through acolumn (1=50 cm, d=2 cm) of basic alumina (Al₂O₃, Aldrich, Brockmann I,about 150 mesh, 58 Å).

[0173] The P(MeFBSEMA-t-BMA) was made in a stirred tube reactor (STR)having the following configuration. It had a capacity of 0.94 L andconsisted of five jacketed (shell-and-tube) glass sections (Pyrexcylinders). The tube had an inner diameter of 3.01 cm and an outerdiameter of 3.81 cm. The shell had a diameter of 6.4 cm. All fivesections were 25.4 cm long. The sections were joined together with polyvinyl chloride (PVC) connector disks. The STR was closed off at thefront with a polytetrafluoroethylene (PTFE) disk and at the end with aPVC disk. Extending through the center of the joined cylinders was a0.95 cm diameter stainless steel shaft suspended along the cylinder axisby shaft alignment pins. To the shaft were affixed 30 detachablerectangular stainless steel paddles with approximately 2.1 cm betweeneach paddle. The paddles were 1.6 mm thick, 1.91 cm wide, and 2.54 cmlong. Each section contained six paddles. The shaft was attached to a1/14 hp variable speed motor and driven at approximately 125 rpm. Heattransfer was accomplished by attachment of recirculators to the jackets.All zones were heated or cooled with water. Zones 1 and 2 were attachedin series so that they were controlled at the same temperature by arecirculator (Model 9105, Fischer Scientific, Hanover Park, Ill.). Zone1 was heated/cooled in a co-current manner while zone 2 was done in acounter-current fashion. Zone 3 was independently controlled using aseparate recirculator (Model RTE 110, Thermo Neslab, Portsmouth, N.H.)and was heated/cooled in a counter-current manner. Zones 4 and 5 wereattached in series so that they were controlled at the same temperatureby a temperature controller (Model M3, MGW Lauda Lauda-Königshofen,Germany) and were heated/cooled in a counter-current manner.

[0174] The P(MeFBSEMA-t-BMA) material was made in the following manner.Purified t-BMA monomer (fed at a rate of 12 ml/min by a reciprocatingpiston pump), cyclohexane (fed at a rate of 17 ml/min by a reciprocatingpiston pump), and the initiator slurry in cyclohexane (pumped at a rateof 10 ml/min by a reciprocating piston pump) were fed into the firstzone of the STR. A color change from clear to light green was observedin zone 1 when the initiator solution contacted the monomer. Thetemperature of the reaction mixture in each of the 5 zones of the STRwas individually maintained at: #1=30° C., #2=30° C., #3=25° C., #4=25°C., and #5=25° C. The reaction mixture flowed through the first fourzones facilitated by stirring paddles along the reaction path.Polymerization continued to substantially 100% completion by the end ofzone 4, thereby forming a “living” poly(t-butyl methacrylate) reaction(P(t-BMA)) homopolymer.

[0175] Then the homopolymer was made into a block copolymer by feedingthe MeFBSEMA solution into zone 5 of the STR, using a reciprocatingpiston pump at a rate of 7 ml/min, which reacted with (P(t-BMA)). Theoverall solids content after both polymerization reactions was about29.7 wt %. The total residence time for the reactions was.about 20minutes. The result was (P(MeFBSEMA-t-BMA)) block copolymer with a moleratio MeFBSEMA to t-BMA of 17 to 83, M_(n) of 8.2×104 and a PDI of 1.97.

[0176] P(MeFBSEMA-t-BMA) (120 g) was loaded into the batch vacuumreactor set at 147° C. and agitated at a speed of 67 rpm to create atorque of 14 Nm. A vacuum of about 4.0 kPa (30 torr) was applied for 5minutes to evaporate any residual solvent. The batch temperature of thereactor was increased to 160° C. Then p-toluenesulfonic acid monohydrate(1 g in 10 ml THF) was siphoned into the reactor and the internal vacuumof the reactor was re-established at about 4.0 kPa. After 15 minutes,the color of the modified starting material, P(MeFBSEMA-t-BMA), hadchanged from yellow to dark brown, and the measured torque had increasedto 17 Nm. At this point, the contents of the reactor were sampled foranalysis and removed from the reactor.

[0177] Samples were tested by Infrared Spectroscopy, which confirmedthat hydrolysis had occurred. The spectra illustrated IR resonances (at1802 cm⁻¹ and 1760 cm⁻¹) indicative of the formation of anhydridefunctionalities and the presence of methacrylic acid at 1709 cm⁻¹.

Example 12 Batch Synthesis of poly(styrene-b-methacrylicanhydride/acid-b-2-(N-methylperfluorobutanesulfonamido)ethylMethacrylate)) via the p-toluenesulfonic Acid Catalyzed Modification ofpoly(styrene-b-t-butylmethacrylate-b-2-(N-methylperfluorobutanesulfonamido)ethyl Methacrylate(P(S-t-BMA-MeFBSEMA)).

[0178] This example illustrates that semifluorinated methacrylicanhydride/acid triblocks can be made via the use of the vacuum reactor.

[0179] The P(S-t-BMA-MeFBSEMA) material was made by the method describedin Example 11. An initiator slurry was prepared by mixing 115 g of 1.3 Msec-butyl lithium solution with 3000 g of dry, oxygen-free cyclohexane,with stirring, at room temperature. A 26 wt % solution of MeFBSEMA intoluene was prepared by dissolving 260 g of MeFBSEMA in 962 ml oftoluene. A 2.5 wt % solution of 1,1′-diphenylethylene in cyclohexane,was prepared by mixing 33 g of 1,1′-diphenylethylene in 1273 g ofpre-purified cyclohexane.

[0180] Purified styrene monomer (fed at a rate of 5.5 ml/min by areciprocating piston pump), cyclohexane (fed at a rate of 11 ml/min by areciprocating piston pump), and the initiator slurry in cyclohexane(pumped at a rate of 10 ml/min by a reciprocating piston pump) were fedinto the first zone of the STR. A color change from clear to orange wasobserved in zone 1 when the initiator solution contacted the monomer.The temperature of the reaction mixture in each of the 5 zones of theSTR was individually maintained at: #1=53° C., #2=53° C., #3=52° C.,#4=47° C., and #5=25° C.

[0181] The materials flowed through the first zone forming a “living”polystyrene reaction mixture. At the start of zone 2, the 2.5 wt %solution of 1,1′-diphenylethylene in cyclohexane was added by areciprocating piston pump (at a rate of 4.4 ml/min) to the “living”polystyrene reaction mixture, resulting in a1,1′-diphenylethylene-modified polystyrenyl chain.

[0182] At the start of zone 3, purified t-BMA monomer (fed at a rate of5.5 ml/min by a reciprocating piston pump) was added to the1,1′-diphenylethylene-modified polystyryl chain and a color change fromburgundy to light green was observed, indicative of a “living”poly(t-butyl methacrylate) chain.

[0183] At the start of zone 5 was added a 26 wt % solution of MeFBSEMAin toluene (by a reciprocating piston pump at a rate of 2.2 ml/min)which reacted with (P(t-BMA)) resulting in the formation of aP(S-t-BMA-MeFBSEMA) triblock copolymer. The overall solids content ofthis polymerization reaction was about 31 wt %. The total residence timefor these reactions was about 29 minutes. The result was(P(MeFBSEMA-t-BMA)) block copolymer with a mole ratio of PS to t-BMA toMeFBSEMA of 57.3 to 38.8 to 4.0 and M_(n) of 3.5×104, with PDI of 1.9.

[0184] The P(S-t-BMA-MeFBSEMA) materials were collected in 1 gallonglass jars, concentrated under reduced pressure in a vacuum oven, andprecipitated by adding the viscous solutions to methanol.

[0185] P(S— t-BMA-MeFBSEMA) (150 g) was loaded into the Batch VacuumReactor set at 160° C. and agitated at a speed of 67 rpm to create atorque of 18 Nm. A vacuum of about 533 Pa (4 torr) was applied for 5minutes to evaporate any possible residual solvent. The batchtemperature of the kneader was increased to 170° C. P-toluenesulfonicacid monohydrate (1 g in 10 ml THF) was siphoned into the reactor andthe internal vacuum of the reactor was re-established at about 533 Pa.After 20 minutes the color of the modified starting material P(S—t-BMA-MeFBSEMA) had changed from white to dark brown, and the measuredtorque had increased to 31 Nm. At this point, the contents of thereactor were sampled for analysis and removed from the reactor.

[0186] Samples were tested by Infrared Spectroscopy, which confirmedthat deesterification had occurred. The spectra illustrated IRresonances indicative of the formation of anhydride functionalities at1802 cm⁻¹ and 1760 cm⁻¹ and the presence of methacrylic acid at 1709cm⁻¹.

Example 13 Batch Synthesis of Hydrogenated poly(isoprene-methacrylicacid/anhydride) via the p-toluenesulfonic Acid CatalyzedDeesterification of Hydrogenated poly(isoprene-t-butyl methacrylate)

[0187] This example illustrates the deesterification of hydrogenatedpolyisoprene or polyolefin based block copolymer systems, such aspolypropylene or polybutylene, and that the reaction products of thedescribed process can be controlled by variation of the residence timefor the reaction.

[0188] Example 13A is hydrogenated poly(isoprene-t-butyl methacrylate)made as follows would be suitable for the deesterification reaction:

[0189] A solution of poly(isoprene-t-butyl methacrylate) (4.3 g) incyclohexane (500 ml) is added to a 2L stirred batch reactor (availableas 316SS from pressure Products, Inc., Westminster, Pa.). To thissolution was added 5% Palladium on BaSO₄ (5.5 g) (available from StremChemicals, Newburyport, Mass.) and the reactor was purged with nitrogenfor 15 minutes. The reactor headspace was evacuated and charged with689.5 kPa(100 psi) of hydrogen gas. The reactor was heated to 105° C. atwhich point the pressure in the reactor increased to 3447 kPa (500 psi).The reactor was stirred at this temperature for 12 hrs, after which thereactor was vented to remove hydrogen. The catalyst was filtered offthrough a 1 μm filter and the polymer was recovered by precipitation inmethanol. Table 8 shows the composition of the resulting material. TABLE8 Hydrogenated PI 1,2-PI 3,4-PI 1,4-PI t-BMA Example mole % mole % mole% mole % mole % 13A 47.7 1.0 19.5 20.6 11.2

[0190] Examples 13B and 13C were the materials actually used for thisexample. They were prepared by Pressure Chemical Co. (Pittsburgh, Pa.),using a proprietary hydrogenation method. According to the PressureChemical method, the Poly(isoprene)-based systems were dissolved andloaded into agitated Parr vessels. After initial nitrogen sparging,these solutions were pressurized with hydrogen, agitated and heated tothe targeted temperature. Table 9 summarizes the composition of thestarting materials and the composition and properties of the resultinghydrogenated materials. TABLE 9 Saturated Unsaturated Starting PolymerCyclohexane Toluene M_(n) Isoprene Isoprene TBMA Ex. Material (grams)(grams) (grams) (×10⁴) PDI (mole %) (mole %) (mole %) 13B PI-TBMA 75 500 897 8.39 1.64 62.8 26.4 10.8 13C PI-TBMA 75 500 1428 7.77 1.65 55.132.2 12.7

[0191] The hydrogenated poly(isoprene)- t-butyl methacrylate (60 g) ofexample 13C was loaded into the batch vacuum reactor described inExample 1, set at 140° C., and agitated at a speed of 68 rpm to create atorque of 16 Nm. A vacuum of about 6.6 kPa (50 torr) was applied for 5minutes to evaporate any solvent. The batch temperature of the reactorwas increased to 148° C., p-toluenesulfonic acid monohydrate (0.5 g in10 ml THF) was siphoned into the reactor, and the internal vacuum of thereactor was re-established at about 6.6 kPa. After 35 minutes, the colorof the starting material, PPBI-t-BMA, had changed from yellow to darkbrown, indicating a modification, and the measured torque had increasedto 17 Nm. At this point, samples of the contents of the reactor weretaken for analysis.

[0192] The samples were tested by Infrared Spectroscopy, which confirmedthat deesterification had occurred. The spectra illustrated IRresonances indicative of the formation of anhydride functionalities at1800 cm⁻¹ and 1758 cm⁻¹ and the presence of methacrylic acid at 1711cm⁻¹.

[0193] The reaction was allowed to continue for an additional 35 minutes(total reaction time of 70 minutes). Samples were again taken and testedby Infrared Spectroscopy, which confirmed that deesterification hadoccurred. The spectra illustrated IR resonances indicative of theformation of anhydride functionalities at 1800 cm⁻¹ and 1758 cm⁻¹ and nomethacrylic acid moieties were observed, indicating that 100% conversionhad occurred.

Example 14 Batch synthesis of hydrogenated poly(isoprene-b-methacrylicacid) via the p-toluenesulfonic acid catalyzed solution deesterificationof hydrogenated poly(isoprene-b t-butyl methacrylate).

[0194] This example illustrates the desterification of hydrogenatedpolyisoprene To a stirred solution of hydrogenated poly(isoprene-bt-butyl methacrylate) (3.6 g) in toluene (50 ml) was addedp-toluenesulfonic acid (0.05 g). The reaction mixture was heated to 80°C. for 8 hrs. Samples were tested by Infrared Spectroscopy, whichconfirmed that deesterification had occurred. The spectra illustrated IRresonances indicative of the formation of methacrylic acid at 1709 cm⁻¹.

[0195] Objects and advantages of this invention are further illustratedby the following examples. The particular materials and amounts thereof,as well as other conditions and details, recited in these examplesshould not be used to unduly limit this invention.

We claim:
 1. A method for modifying a polymer comprising: providing amixing apparatus having a high shear environment and devolatilizationcapabilities, introducing into the apparatus a composition containing atleast one polymer that can be modified by a thermally-induced reaction,exposing the composition to the high shear environment at a temperatureof about 100° C. to about 180° C., whereby a thermally-induced reactionoccurs and volatile by-product is removed.
 2. The method of claim 1wherein the composition when introduced into the apparatus comprises 90weight % solids or less.
 3. The method of claim 1 wherein thecomposition comprises at least one polymer that is temperaturesensitive.
 4. The method of claim 1 wherein the thermally-inducedreaction removes at least one protective group to expose a functionalgroup.
 5. The method of claim 4 wherein the exposed functional group iscapable of undergoing a grafting reaction.
 6. The method of claim 4wherein the thermally-induced reaction comprises the elimination ofisobutylene and water from methacrylic and acrylic esters to produce oneor both of acid and anhydride functionalities.
 7. The method of claim 6wherein the polymer includes a fluorinated comonomer.
 8. The method ofclaim 7 wherein the fluorinated comonomer contains at least one mer unithaving the formula

where

represents a bond in a polymerizable or polymer chain; R_(f) is —C₆F₁₃,—C₄F₉, or —C₃F₇; R and R₂ are each independently hydrogen or alkyl of 1to 20 carbon atoms; n is an integer from 2 to 11; and x is an integer ofat least
 1. 9. The method of claim 6 wherein the reaction is catalyzed.10. The method of claim 6 wherein the reaction is acid-catalyzed. 11.The method of claim 4 wherein the thermally-induced reaction comprisesthe elimination of trialkylsilanes from trialkylsiloxy end or side groupcontaining polymers to produce hydroxyl end or side group functionalpolymers.
 12. The method of claim 4 wherein the thermally-inducedreaction comprises the elimination of trialkylsilanes from polymer endor side groups to produce amino end or side group functional polymers.13. The method of claim 4 wherein the thermally-induced reactioncomprises a deesterification reaction to produce hydroxyl- or carboxylicacid-functionalized polymers.
 14. The method of claim 13 wherein thereaction is base-catalyzed.
 15. The method of claim 4 wherein thethermally-induced reaction comprises the elimination of N₂ from acylazides and subsequent rearrangement to form isocyanate functionality.16. The method of claim 4 wherein the functional group is ethylenicallyor acetylenically unsaturated.
 17. The method of claim 16 wherein thethermally-induced reaction comprises the elimination of benzenesulfenicacid from poly(vinyl phenyl sulfoxide) to producepolyacetylene-containing polymers.
 18. The method of claim 4 wherein thethermally-induced reaction comprises the elimination of trialkylsilanesfrom trialkylsilthiane end or sidegroup containing polymers to producethiol end or sidegroup functional polymers.
 19. The method of claim 4wherein the thermally-induced reaction comprises the elimination oftrialkylsilanes from trialkylsilyl-substituted ethynyl monomers, such as2-, 3- and 4-[(trimethylsilyl)-ethynyl]styrenes, producingethynyl-containing side-group or end functionalized polymers.
 20. Themethod of claim 4 further comprising an in situ chemical reaction at thefunctional group.
 21. The method of claim 20 wherein the chemicalreaction comprises forming a graft polymer.
 22. The method of claim 1wherein the mixing apparatus is a high viscosity devolatilizer.
 23. Themethod of claim 1 wherein the mixing apparatus is a devolatilizingkneader.
 24. A composition of matter comprising a controlledarchitecture material comprising at least one diene block and at leastone (meth)acrylic anhydride block.
 25. The composition of matter ofclaim 24 further comprising at least one styrenic block.
 26. Thecomposition of claim 24 comprising a hydrogenatedpoly(diene-(meth)acrylic anhydride) controlled architecture material.27. The composition of claim 26 wherein the diene is selected from thegroup consisting of isoprene, butadiene, and cyclohexadiene.
 28. Acomposition of matter comprising a controlled architecture materialcomprising at least one styrenic block and at least one block containingN-methylperfluorobutanesulfonamido.
 29. The composition of claim 28comprising a poly(styrenic-(meth)acrylicanhydride-2-(N-methylperfluorobutanesulfonamido) controlled architecturematerial.
 30. The composition of claim 29 comprising apoly(styrene-(meth)acrylicanhydride-2-(N-methylperfluorobutanesulfonamido) controlled architecturematerial.
 31. The composition of claim 28 comprising apoly(styrenic-(meth)acrylic acid-2-(N-methylperfluorobutanesulfonamido)controlled architecture material.
 32. The composition of claim 31comprising a poly(styrene-(meth)acrylicacid-2-(N-methylperfluorobutanesulfonamido) controlled architecturematerial.
 33. A composition of matter comprising a controlledarchitecture material comprising at least one diene block and at leastone block containing N-methylperfluorobutanesulfonamido.
 34. Thecomposition of claim 33 comprising a poly(diene-(meth)acrylicanhydride-2-(N-methylperfluorobutanesulfonamido) controlled architecturematerial.
 35. The composition of claim 33 comprising apoly(diene-(meth)acrylic acid-2-(N-methylperfluorobutanesulfonamido)controlled architecture material.
 36. A composition of matter comprisinga controlled architecture material comprising at least one diene blockand at least one (meth)acrylic acid co-(meth)acrylic anhydride block.37. The composition of matter of claim 36 further comprising at leastone styrenic block.
 38. The composition of matter of claim 36 furthercomprising at least one perfluoroalkyl (meth)acrylate block containingat least one mer unit having the formula

where

represents a bond in a polymerizable or polymer chain; R_(f) is —C₆F₁₃,—C₄F₉, or —C₃F₇; R and R₂ are each independently hydrogen or alkyl of 1to 20 carbon atoms; n is an integer from 2 to 11; and x is an integer ofat least
 1. 39. A composition of matter comprising at least one styrenicblock, at least one (meth)acrylic acid-co-(meth)acrylic anhydride block,and at least one perfluoroalkyl (meth)acrylate block containing at leastone mer unit having the formula

where

represents a bond in a polymerizable or polymer chain; R_(f) is —C₆F₁₃,—C₄F₉, or —C₃F₇; R and R₂ are each independently hydrogen or alkyl of 1to 20 carbon atoms; n is an integer from 2 to 11; and x is an integer ofat least 1.